Pub Date : 2026-02-15Epub Date: 2025-12-17DOI: 10.1016/j.ssi.2025.117100
Siying Li, Yang Zhang, Lulu Wang, Fan Zhang, Jilin Wang
To prepare anion exchange membranes (AEMs) that exhibit both high conductivity and robust alkaline stability, in this work, chloromethylated polysulfone (CMPSf) was cross-linked with branched polyethyleneimine (BPEI) and quaternized, producing a series of AEMs featuring regionally dense ion clusters. Systematic adjustment the length of the quaternizing reagent enabled the construction of long-range, interconnected ion transport channels, leading to an improved balance between OH− conductivity and dimensional stability. The QPSf-QBPEI8 AEM, which contains hydrophobic chains with eight alkyl carbons, demonstrated a conductivity of 114.96 mS·cm−1 with swelling ratio of 43.5 % at 80 °C. The use of quaternized polyethyleneimine reduces the need for extensive backbone modification. Furthermore, the steric hindrance offered by the hydrophobic chains significantly enhances the alkaline stability of the membranes (84.6 % conductivity retention after 30 days in 6 M KOH). Additionally, the single cell configured with QPSf-QBPEI8 AEM achieved a maximum power density of 502.12 mW cm−2 at 80 °C. These results indicate that QPSf-QBPEI8 exhibits a promising application potential in fuel cells.
为了制备具有高导电性和强碱性稳定性的阴离子交换膜（AEMs），本研究将氯甲基化聚砜（CMPSf）与支链聚乙烯亚胺（BPEI）交联并季铵化，制备了一系列具有区域密集离子簇的AEMs。系统地调整季铵化试剂的长度，可以构建长距离、相互连接的离子传输通道，从而改善OH -电导率和尺寸稳定性之间的平衡。含有8个烷基碳疏水链的QPSf-QBPEI8 AEM在80℃时的电导率为114.96 mS·cm−1，溶胀率为43.5%。季铵化聚乙烯亚胺的使用减少了对骨架进行大量改性的需要。此外，疏水链提供的空间位阻显著提高了膜的碱性稳定性（在6 M KOH中30天后电导率保持84.6%）。此外，配置了QPSf-QBPEI8 AEM的单电池在80°C下实现了502.12 mW cm - 2的最大功率密度。这些结果表明QPSf-QBPEI8在燃料电池中具有良好的应用潜力。
{"title":"High-performance quaternized polysulfone and branched polyethyleneimine anion exchange membranes","authors":"Siying Li, Yang Zhang, Lulu Wang, Fan Zhang, Jilin Wang","doi":"10.1016/j.ssi.2025.117100","DOIUrl":"10.1016/j.ssi.2025.117100","url":null,"abstract":"<div><div>To prepare anion exchange membranes (AEMs) that exhibit both high conductivity and robust alkaline stability, in this work, chloromethylated polysulfone (CMPSf) was cross-linked with branched polyethyleneimine (BPEI) and quaternized, producing a series of AEMs featuring regionally dense ion clusters. Systematic adjustment the length of the quaternizing reagent enabled the construction of long-range, interconnected ion transport channels, leading to an improved balance between OH<sup>−</sup> conductivity and dimensional stability. The QPSf-QBPEI<sub>8</sub> AEM, which contains hydrophobic chains with eight alkyl carbons, demonstrated a conductivity of 114.96 mS·cm<sup>−1</sup> with swelling ratio of 43.5 % at 80 °C. The use of quaternized polyethyleneimine reduces the need for extensive backbone modification. Furthermore, the steric hindrance offered by the hydrophobic chains significantly enhances the alkaline stability of the membranes (84.6 % conductivity retention after 30 days in 6 M KOH). Additionally, the single cell configured with QPSf-QBPEI<sub>8</sub> AEM achieved a maximum power density of 502.12 mW cm<sup>−2</sup> at 80 °C. These results indicate that QPSf-QBPEI<sub>8</sub> exhibits a promising application potential in fuel cells.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"435 ","pages":"Article 117100"},"PeriodicalIF":3.3,"publicationDate":"2026-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145765747","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-02-15Epub Date: 2025-12-27DOI: 10.1016/j.ssi.2025.117106
Samuel Merk , Jan Meyer , David Müller , Thomas F. Fässler
Solid electrolytes are a key feature of all-solid-state batteries, which represent advanced energy storage systems. The investigation of electrochemical properties of promising materials is essential for the development of new compounds. Herein, we report a simple and compact polyether ether ketone (PEEK)-based cell for the analysis of air and moisture sensitive solid electrolytes, including brittle microcrystalline powders or tapes. The cell exhibits low intrinsic capacitance, enabling impedance spectroscopy across the full frequency range without interfering features and applicable for a large temperature range from −70 °C to 80 °C. Controlled fabrication and measurement pressures improve the reproducibility of impedance measurements. Using polytetrafluoroethylene samples of varying thickness, this stray capacitance is measured and determined. Temperature-dependent electrochemical impedance spectroscopy of Li6PS5Cl/hydrogenated nitrile butadiene rubber (HNBR) sheets, conducted between −70 °C and 80 °C, demonstrates the cell durability and the high reproducibility of impedance measurements. Furthermore, the airtightness and experimental consistency were maintained even after 250 h of operation. Finally, we highlight the importance of low intrinsic capacitance by successfully resolving the bulk and grain contributions in Li6PS5Cl.
{"title":"A compact cell for electrochemical investigations of solid-state materials","authors":"Samuel Merk , Jan Meyer , David Müller , Thomas F. Fässler","doi":"10.1016/j.ssi.2025.117106","DOIUrl":"10.1016/j.ssi.2025.117106","url":null,"abstract":"<div><div>Solid electrolytes are a key feature of all-solid-state batteries, which represent advanced energy storage systems. The investigation of electrochemical properties of promising materials is essential for the development of new compounds. Herein, we report a simple and compact polyether ether ketone (PEEK)-based cell for the analysis of air and moisture sensitive solid electrolytes, including brittle microcrystalline powders or tapes. The cell exhibits low intrinsic capacitance, enabling impedance spectroscopy across the full frequency range without interfering features and applicable for a large temperature range from −70 °C to 80 °C. Controlled fabrication and measurement pressures improve the reproducibility of impedance measurements. Using polytetrafluoroethylene samples of varying thickness, this stray capacitance is measured and determined. Temperature-dependent electrochemical impedance spectroscopy of Li<sub>6</sub>PS<sub>5</sub>Cl/hydrogenated nitrile butadiene rubber (HNBR) sheets, conducted between −70 °C and 80 °C, demonstrates the cell durability and the high reproducibility of impedance measurements. Furthermore, the airtightness and experimental consistency were maintained even after 250 h of operation. Finally, we highlight the importance of low intrinsic capacitance by successfully resolving the bulk and grain contributions in Li<sub>6</sub>PS<sub>5</sub>Cl.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"435 ","pages":"Article 117106"},"PeriodicalIF":3.3,"publicationDate":"2026-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145881420","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-02-15Epub Date: 2025-12-24DOI: 10.1016/j.ssi.2025.117104
D. Narsimulu, Ramkumar Balasubramaniam, Kwang-Sun Ryu
The Li7P3S11 sulfur solid electrolyte is a promising candidate for developing safe and high-performance all solid-state lithium-ion batteries (ASSLIBs). Air-sensitivity and poor electrode/electrolyte interfacial compatibility remain major bottlenecks for ASSLIBs. Despite the use of various strategies to address these issues, a highly effective solution is still required for ASSLIBs. For the first time, selenium (Se) anion is introduced as a dopant for the Li7P3S11-type sulfide electrolyte, which can simultaneously enhance Li-ion conductivity and lower the interfacial resistance between the NCM811 cathode and the electrolyte. A novel series of Li7P3S11-xSex sulfur SEs (x = 0, 0.025, 0.05, 0.075, 0.1, 0.125, & 0.15) was synthesized by a high energy ball milling method, and the Li7P3S10.9Se0.1 SEs demonstrated an excellent Li-ion conductivity of 2.48 mS cm−1 at 25 °C. XRD data and EDS mapping images confirm successful Se doping, which contributes to lattice expansion and improves Li-ion conductivity of the electrolyte. Notably, Se substitution at S sites significantly improves the moisture stability of the newly developed sulfide solid electrolyte. Furthermore, Li plating/stripping experiments show that Li7P3S10.9Se0.1 provides improved interfacial compatibility with lithium metal. Consequently, the assembled Li-In/ Li7P3S10.9Se0.1/NCM811 solid state battery retained a high discharge capacity of 82 mAh g−1 at a 0.1C rate and exhibited superior capacity retention compared to the undoped solid state battery. The selenium (Se) anion doping approach presents a promising strategy to achieve high ionic conductivity, air stability, and improved electrode/electrolyte interfacial properties for high-performance ASSLIBs.
Li7P3S11硫固体电解质是开发安全、高性能全固态锂离子电池（asslib）的理想材料。空气敏感性和电极/电解质界面兼容性差仍然是asslib的主要瓶颈。尽管使用了各种策略来解决这些问题，但asslib仍然需要一个高效的解决方案。首次在li7p3s11型硫化物电解液中引入硒阴离子作为掺杂剂，可同时提高锂离子电导率，降低NCM811阴极与电解液之间的界面电阻。采用高能球磨法合成了一系列新型的Li7P3S11-xSex硫醚（x = 0,0.025, 0.05, 0.075, 0.1, 0.125, & 0.15）， Li7P3S10.9Se0.1 se在25°C时具有2.48 mS cm−1的优异锂离子电导率。XRD数据和EDS图谱证实了Se掺杂的成功，这有助于电解质的晶格膨胀和锂离子电导率的提高。值得注意的是，S位的Se取代显著提高了新开发的硫化物固体电解质的水分稳定性。此外，锂电镀/剥离实验表明，Li7P3S10.9Se0.1与锂金属的界面相容性得到了改善。结果表明，组装后的Li-In/ Li7P3S10.9Se0.1/NCM811固态电池在0.1C倍率下保持了82 mAh g−1的高放电容量，与未掺杂的固态电池相比，具有更好的容量保持能力。硒（Se）阴离子掺杂方法为实现高性能asslib的高离子电导率、空气稳定性和改善电极/电解质界面性能提供了一种有前途的策略。
{"title":"Anion engineering enhances the electrochemical performance of Li7P3S11 solid electrolyte","authors":"D. Narsimulu, Ramkumar Balasubramaniam, Kwang-Sun Ryu","doi":"10.1016/j.ssi.2025.117104","DOIUrl":"10.1016/j.ssi.2025.117104","url":null,"abstract":"<div><div>The Li<sub>7</sub>P<sub>3</sub>S<sub>11</sub> sulfur solid electrolyte is a promising candidate for developing safe and high-performance all solid-state lithium-ion batteries (ASSLIBs). Air-sensitivity and poor electrode/electrolyte interfacial compatibility remain major bottlenecks for ASSLIBs. Despite the use of various strategies to address these issues, a highly effective solution is still required for ASSLIBs. For the first time, selenium (Se) anion is introduced as a dopant for the Li<sub>7</sub>P<sub>3</sub>S<sub>11</sub>-type sulfide electrolyte, which can simultaneously enhance Li-ion conductivity and lower the interfacial resistance between the NCM811 cathode and the electrolyte. A novel series of Li<sub>7</sub>P<sub>3</sub>S<sub>11-<em>x</em></sub>Se<sub><em>x</em></sub> sulfur SEs (<em>x</em> = 0, 0.025, 0.05, 0.075, 0.1, 0.125, & 0.15) was synthesized by a high energy ball milling method, and the Li<sub>7</sub>P<sub>3</sub>S<sub>10.9</sub>Se<sub>0.1</sub> SEs demonstrated an excellent Li-ion conductivity of 2.48 mS cm<sup>−1</sup> at 25 °C. XRD data and EDS mapping images confirm successful Se doping, which contributes to lattice expansion and improves Li-ion conductivity of the electrolyte. Notably, Se substitution at S sites significantly improves the moisture stability of the newly developed sulfide solid electrolyte. Furthermore, Li plating/stripping experiments show that Li<sub>7</sub>P<sub>3</sub>S<sub>10.9</sub>Se<sub>0.1</sub> provides improved interfacial compatibility with lithium metal. Consequently, the assembled Li-In/ Li<sub>7</sub>P<sub>3</sub>S<sub>10.9</sub>Se<sub>0.1</sub>/NCM811 solid state battery retained a high discharge capacity of 82 mAh g<sup>−1</sup> at a 0.1C rate and exhibited superior capacity retention compared to the undoped solid state battery. The selenium (Se) anion doping approach presents a promising strategy to achieve high ionic conductivity, air stability, and improved electrode/electrolyte interfacial properties for high-performance ASSLIBs.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"435 ","pages":"Article 117104"},"PeriodicalIF":3.3,"publicationDate":"2026-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145838301","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-02-15Epub Date: 2025-12-22DOI: 10.1016/j.ssi.2025.117105
Maria Bolar , William T. Andrews , Zachariah Bess , Laura Bonsmann , Constantin Ciocanel , Cindy C. Browder
The drive for safer and longer-lasting power storage devices has centered on the development of solid electrolytes. Our group has developed a PEO-based quasi-solid polymer electrolyte (QSPE) that utilizes a hyperbranched polymer host, generated by in situ polymerization, that imparts mechanical strength while maintaining the amorphous character required for electrolyte conductivity. In this report, a LiCl-in-H2O QSPE was prepared and characterized. By replacing the traditional QSPE carbonate plasticizer with water, the use of lower-cost, reduced-toxicity electrolytic salts is realized, leading to a safer hydrogel electrolyte. The LiCl-in-H2O QSPE exhibited competitive room-temperature bulk conductivity (5.5 × 10−4 S/cm), with mechanical strength (0.40 MPa shear storage modulus) suitable for flexible electronics. Notably, the LiCl-in-H2O QSPE has a lower cost ($0.60 per g) and acute toxicity estimate (2120 mg/kg) relative to traditional formulations. In structural supercapacitors, the hydrogel QSPE enables specific capacitance 23.11 mF/g of and energy density of 2.05 × 10−3 Wh/kg. This work validates the combination of a hyperbranched polymer host with an aqueous lithium salt as a promising and cost-effective strategy for development of safer, next-generation lithium-based energy storage devices.
{"title":"Cost-effective low-toxicity hydrogel quasi-solid polymer electrolyte (QSPE) with a PEO-based hyperbranched polymer host","authors":"Maria Bolar , William T. Andrews , Zachariah Bess , Laura Bonsmann , Constantin Ciocanel , Cindy C. Browder","doi":"10.1016/j.ssi.2025.117105","DOIUrl":"10.1016/j.ssi.2025.117105","url":null,"abstract":"<div><div>The drive for safer and longer-lasting power storage devices has centered on the development of solid electrolytes. Our group has developed a PEO-based quasi-solid polymer electrolyte (QSPE) that utilizes a hyperbranched polymer host, generated by in situ polymerization, that imparts mechanical strength while maintaining the amorphous character required for electrolyte conductivity. In this report, a LiCl-in-H<sub>2</sub>O QSPE was prepared and characterized. By replacing the traditional QSPE carbonate plasticizer with water, the use of lower-cost, reduced-toxicity electrolytic salts is realized, leading to a safer hydrogel electrolyte. The LiCl-in-H<sub>2</sub>O QSPE exhibited competitive room-temperature bulk conductivity (5.5 × 10<sup>−4</sup> S/cm), with mechanical strength (0.40 MPa shear storage modulus) suitable for flexible electronics. Notably, the LiCl-in-H<sub>2</sub>O QSPE has a lower cost ($0.60 per g) and acute toxicity estimate (2120 mg/kg) relative to traditional formulations. In structural supercapacitors, the hydrogel QSPE enables specific capacitance 23.11 mF/g of and energy density of 2.05 × 10<sup>−3</sup> Wh/kg. This work validates the combination of a hyperbranched polymer host with an aqueous lithium salt as a promising and cost-effective strategy for development of safer, next-generation lithium-based energy storage devices.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"435 ","pages":"Article 117105"},"PeriodicalIF":3.3,"publicationDate":"2026-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145838302","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-02-01Epub Date: 2025-12-12DOI: 10.1016/j.ssi.2025.117103
Jordan A. Barr , Scott P. Beckman , Brandon C. Wood , Liwen F. Wan
Al-doped garnet Li7La3Zr2O12 solid-electrolyte and LiCoO2 cathode are promising choices as catholyte materials in all solid-state Li batteries, however, interdiffusion of Al is commonly evident during high-temperature processing and electrochemical cycling. To address the impact of Al interdiffusion on Li+ transport properties in LiCoO2, we carried out a systematic evaluation of Al doping on Li+ diffusion barriers in LiCoO2 using first-principles based methods. Following the monovacancy diffusion mechanism, Al-doping (primarily at the Co site) is found to improve Li diffusion kinetics in the LiCoO2 lattice due to favorable CoO6 octahedral distortion experienced at the transition states. However, when considering the previously established dominant divacancy diffusion mechanism, slower Li diffusion is generally expected. In addition, a broad variation of Li diffusion barriers is observed upon Al doping, which suggests the system may suffer from non-uniform Li incorporation and diffusion that adversely affects its rate capacity during cycling. In summary, this work highlights, for the rational design of catholyte of all solid-state batteries, special attention may need to be paid to address the potential impact of non-intentional doping induced during processing on the overall electrochemical performance of the catholyte.
{"title":"First-principles elucidation of the effects of Al-doping on Li-ion diffusion in LiCoO2","authors":"Jordan A. Barr , Scott P. Beckman , Brandon C. Wood , Liwen F. Wan","doi":"10.1016/j.ssi.2025.117103","DOIUrl":"10.1016/j.ssi.2025.117103","url":null,"abstract":"<div><div>Al-doped garnet Li<sub>7</sub>La<sub>3</sub>Zr<sub>2</sub>O<sub>12</sub> solid-electrolyte and LiCoO<sub>2</sub> cathode are promising choices as catholyte materials in all solid-state Li batteries, however, interdiffusion of Al is commonly evident during high-temperature processing and electrochemical cycling. To address the impact of Al interdiffusion on Li<sup>+</sup> transport properties in LiCoO<sub>2</sub>, we carried out a systematic evaluation of Al doping on Li<sup>+</sup> diffusion barriers in LiCoO<sub>2</sub> using first-principles based methods. Following the monovacancy diffusion mechanism, Al-doping (primarily at the Co site) is found to improve Li diffusion kinetics in the LiCoO<sub>2</sub> lattice due to favorable CoO<sub>6</sub> octahedral distortion experienced at the transition states. However, when considering the previously established dominant divacancy diffusion mechanism, slower Li diffusion is generally expected. In addition, a broad variation of Li diffusion barriers is observed upon Al doping, which suggests the system may suffer from non-uniform Li incorporation and diffusion that adversely affects its rate capacity during cycling. In summary, this work highlights, for the rational design of catholyte of all solid-state batteries, special attention may need to be paid to address the potential impact of non-intentional doping induced during processing on the overall electrochemical performance of the catholyte.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"434 ","pages":"Article 117103"},"PeriodicalIF":3.3,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145748359","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-02-01Epub Date: 2025-12-16DOI: 10.1016/j.ssi.2025.117101
Darshilkumar N. Chhatrodiya , Sunil Kumar , Santanu De , Shobit Omar
A transmission-line model is developed to predict the oxygen flux through ceramic-based mixed ionic–electronic conducting (MIEC) membranes for air separation. The model is derived from the oxygen vacancy continuity equation, incorporating surface reaction kinetics as a sink term, and yields an impedance expression analogous to the de Levie transmission-line model widely applied to porous SOFC electrodes. To validate this approach, a novel MIEC ceramic composite comprising 65 wt% Gd0.1Ce0.9O2-δ (GDC) and 35 wt% SrFe0.9Ti0.1O3-δ (SFTO) is synthesized. Symmetrical cells are fabricated using 65GDC–35SFTO electrodes with a zirconia electrolyte and a GDC buffer-layer. Electrochemical impedance spectroscopy (EIS) is performed across a temperature range of 600–950 °C under varying pO2, and the electrode response is simulated employing the transmission-line model to decouple surface exchange resistance, ionic diffusion resistance, and chemical capacitance. A dense MIEC membrane coated on both sides with a porous layer of 65GDC–35SFTO is tested for oxygen permeation under different pO2 gradients. An oxygen flux of 0.61 ml.cm-2.min-1 is achieved at 950 °C, which remains stable for over 200 h. Using the developed theoretical resistance model, the resistances of the porous and dense MIEC layers are evaluated, enabling a reliable prediction of the steady-state oxygen permeation flux.
{"title":"Resistance-based transmission-line model for O2 flux prediction in Gd0.1Ce0.9O2-δ–SrFe0.9Ti0.1O3-δ composite membranes","authors":"Darshilkumar N. Chhatrodiya , Sunil Kumar , Santanu De , Shobit Omar","doi":"10.1016/j.ssi.2025.117101","DOIUrl":"10.1016/j.ssi.2025.117101","url":null,"abstract":"<div><div>A transmission-line model is developed to predict the oxygen flux through ceramic-based mixed ionic–electronic conducting (MIEC) membranes for air separation. The model is derived from the oxygen vacancy continuity equation, incorporating surface reaction kinetics as a sink term, and yields an impedance expression analogous to the de Levie transmission-line model widely applied to porous SOFC electrodes. To validate this approach, a novel MIEC ceramic composite comprising 65 wt% Gd<sub>0.1</sub>Ce<sub>0.9</sub>O<sub>2-<em>δ</em></sub> (GDC) and 35 wt% SrFe<sub>0.9</sub>Ti<sub>0.1</sub>O<sub>3-<em>δ</em></sub> (SFTO) is synthesized. Symmetrical cells are fabricated using 65GDC–35SFTO electrodes with a zirconia electrolyte and a GDC buffer-layer. Electrochemical impedance spectroscopy (EIS) is performed across a temperature range of 600–950 °C under varying pO<sub>2</sub>, and the electrode response is simulated employing the transmission-line model to decouple surface exchange resistance, ionic diffusion resistance, and chemical capacitance. A dense MIEC membrane coated on both sides with a porous layer of 65GDC–35SFTO is tested for oxygen permeation under different pO<sub>2</sub> gradients. An oxygen flux of 0.61 ml.cm<sup>-</sup><sup>2</sup>.min<sup>-1</sup> is achieved at 950 °C, which remains stable for over 200 h. Using the developed theoretical resistance model, the resistances of the porous and dense MIEC layers are evaluated, enabling a reliable prediction of the steady-state oxygen permeation flux.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"434 ","pages":"Article 117101"},"PeriodicalIF":3.3,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145797675","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-02-01Epub Date: 2025-12-05DOI: 10.1016/j.ssi.2025.117095
Vincenzo J. Musicó , Noah P. Holzapfel , Menghang Wang , Wan-Yu Tsai , Tatiana Proksch , Boris Kozinsky , Nina Balke , Veronica Augustyn
The demand for high-energy and high-power energy storage devices motivates the search for electrode materials with both high capacity and fast ion transport. One class of materials that could achieve such performance are oxides containing crystallographic shear (CS) planes. Here, we compare the structural dynamics of tungsten trioxide (WO3) and its oxygen deficient, CS Magnéli phase (WO2.9) during electrochemical insertion of H+ and Li+ ions using a combined experimental and computational study. We found that WO3 inserts more H+ per formula unit than WO2.9 yet operando electrochemical atomic force microscopy shows more deformation in WO2.9 than WO3 per inserted H+. In contrast, WO2.9 accommodates ∼0.2 more Li+ per formula unit than WO3 and has higher Li+ diffusion and better rate capability. Operando electrochemical X-ray diffraction shows that Li+ insertion into WO2.9 leads to lattice contraction and 5 % volume change up to Li0.6WO2.9 followed by a zero-strain region up to Li1.4WO2.9. We find that the presence of CS planes, and its effect on octahedral tilting, lead to different outcomes depending on the inserting ion: while octahedral tilting and lack of CS planes promote H+ insertion into WO3, their absence in WO2.9 favor Li+ insertion. We propose that the presence of CS planes impart structural rigidity, enabling higher capacity, improved rate capability, and enhanced cyclability during Li+ insertion but remove favorable bridging oxygen sites for H+ insertion.
{"title":"Ion-dependent electrochemical behavior in shear-structured tungsten oxides","authors":"Vincenzo J. Musicó , Noah P. Holzapfel , Menghang Wang , Wan-Yu Tsai , Tatiana Proksch , Boris Kozinsky , Nina Balke , Veronica Augustyn","doi":"10.1016/j.ssi.2025.117095","DOIUrl":"10.1016/j.ssi.2025.117095","url":null,"abstract":"<div><div>The demand for high-energy and high-power energy storage devices motivates the search for electrode materials with both high capacity and fast ion transport. One class of materials that could achieve such performance are oxides containing crystallographic shear (CS) planes. Here, we compare the structural dynamics of tungsten trioxide (WO<sub>3</sub>) and its oxygen deficient, CS Magnéli phase (WO<sub>2.9</sub>) during electrochemical insertion of H<sup>+</sup> and Li<sup>+</sup> ions using a combined experimental and computational study. We found that WO<sub>3</sub> inserts more H<sup>+</sup> per formula unit than WO<sub>2.9</sub> yet operando electrochemical atomic force microscopy shows more deformation in WO<sub>2.9</sub> than WO<sub>3</sub> per inserted H<sup>+</sup>. In contrast, WO<sub>2.9</sub> accommodates ∼0.2 more Li<sup>+</sup> per formula unit than WO<sub>3</sub> and has higher Li<sup>+</sup> diffusion and better rate capability. Operando electrochemical X-ray diffraction shows that Li<sup>+</sup> insertion into WO<sub>2.9</sub> leads to lattice contraction and 5 % volume change up to Li<sub>0.6</sub>WO<sub>2.9</sub> followed by a zero-strain region up to Li<sub>1.4</sub>WO<sub>2.9</sub>. We find that the presence of CS planes, and its effect on octahedral tilting, lead to different outcomes depending on the inserting ion: while octahedral tilting and lack of CS planes promote H<sup>+</sup> insertion into WO<sub>3</sub>, their absence in WO<sub>2.9</sub> favor Li<sup>+</sup> insertion. We propose that the presence of CS planes impart structural rigidity, enabling higher capacity, improved rate capability, and enhanced cyclability during Li<sup>+</sup> insertion but remove favorable bridging oxygen sites for H<sup>+</sup> insertion.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"434 ","pages":"Article 117095"},"PeriodicalIF":3.3,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145692512","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-02-01Epub Date: 2025-12-03DOI: 10.1016/j.ssi.2025.117097
E. Bonnet , M.C. Steil , J. Fouletier , L. Gaillard , B. Rousseau , C. Jourde , J.-M. Bassat , P.-M. Geffroy
Optimizing the performance of Solid Oxide Fuel Cells (SOFCs) or Solid Oxide Electrolysis Cells (SOECs) necessitates a thorough understanding of the electrolytes' transport properties under the device's operating conditions, whether through experimental data or established transport laws. This study investigates the electrical properties of Gd-doped ceria as a potential electrolyte material for SOFC applications. The electrical behavior of Gd-doped ceria was analyzed over a broad range of oxygen partial pressures (from 10−36 to 1 bar) and temperatures (200 °C to 900 °C) to establish the Patterson diagram, i.e., the variation of the total electrical conductivity as a function of the oxygen partial pressure (on logarithmic scales) for various temperatures. Additionally, the average transport number of the Gd-doped ceria electrolyte was evaluated under varying oxygen partial pressure gradients and temperatures using a specific semi-permeation method and compared with data derived from the Patterson diagram. The results collected in this study indicate that the use of Gd-doped ceria as an SOFC electrolyte requires precise control of oxygen partial pressure (particularly below 10−24 bar at 600 °C) or the hydrogen-to-water ratio at the hydrogen electrode to prevent efficiency degradation of the electrochemical system and to determine optimal operating conditions.
{"title":"Determining the optimal operating conditions of SOFCs electrolytes based on evolution of their electronic transport number with temperature and oxygen partial pressure: A case study of the Ce0.9Gd0.1O2-δ electrolyte","authors":"E. Bonnet , M.C. Steil , J. Fouletier , L. Gaillard , B. Rousseau , C. Jourde , J.-M. Bassat , P.-M. Geffroy","doi":"10.1016/j.ssi.2025.117097","DOIUrl":"10.1016/j.ssi.2025.117097","url":null,"abstract":"<div><div>Optimizing the performance of Solid Oxide Fuel Cells (SOFCs) or Solid Oxide Electrolysis Cells (SOECs) necessitates a thorough understanding of the electrolytes' transport properties under the device's operating conditions, whether through experimental data or established transport laws. This study investigates the electrical properties of Gd-doped ceria as a potential electrolyte material for SOFC applications. The electrical behavior of Gd-doped ceria was analyzed over a broad range of oxygen partial pressures (from 10<sup>−36</sup> to 1 bar) and temperatures (200 °C to 900 °C) to establish the Patterson diagram, i.e., the variation of the total electrical conductivity as a function of the oxygen partial pressure (on logarithmic scales) for various temperatures. Additionally, the average transport number of the Gd-doped ceria electrolyte was evaluated under varying oxygen partial pressure gradients and temperatures using a specific semi-permeation method and compared with data derived from the Patterson diagram. The results collected in this study indicate that the use of Gd-doped ceria as an SOFC electrolyte requires precise control of oxygen partial pressure (particularly below 10<sup>−24</sup> bar at 600 °C) or the hydrogen-to-water ratio at the hydrogen electrode to prevent efficiency degradation of the electrochemical system and to determine optimal operating conditions.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"434 ","pages":"Article 117097"},"PeriodicalIF":3.3,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145692529","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-02-01Epub Date: 2025-12-01DOI: 10.1016/j.ssi.2025.117085
John-Joseph Marie , Jun Chen , Shengda D. Pu , Alex W. Robertson , Robert A. House , Peter G. Bruce
Ion-exchange is an important route to achieve partial or complete substitution of alkali ions into intercalation cathodes for alkali-ion batteries. In Na-ion cathodes, the partial substitution of Na for large, charge dense pillar ions, such as Ca2+, could help alleviate the detrimental structural transitions that these cathodes undergo during desodiation. Typically, ion-exchange is achieved by heating the cathode powder in the presence of a substantial molar excess of alkali halide salt in solution. Here, we successfully demonstrate ion-exchange of Ca2+ for Na+ in Na0.67Mn0.72Mg0.28O2 by simple mechanical mixing of powders with the proper molar amount of CaI2 under ambient conditions. The reaction proceeds in the solid-state at room temperature via the formation of crystalline hydrates of CaI2 which form spontaneously with moisture in the air. Ca2+ is uniformly incorporated into the layered cathode up to a limit of about 0.1 Ca (i.e. Na0.47Ca0.1Mn0.72Mg0.28O2). These findings point to the intriguing possibility of achieving facile room temperature, solid-state ion-exchange in other alkali-ion systems.
{"title":"Room temperature, solid-state Ca ion-exchange in Na0.67Mn0.72Mg0.28O2","authors":"John-Joseph Marie , Jun Chen , Shengda D. Pu , Alex W. Robertson , Robert A. House , Peter G. Bruce","doi":"10.1016/j.ssi.2025.117085","DOIUrl":"10.1016/j.ssi.2025.117085","url":null,"abstract":"<div><div>Ion-exchange is an important route to achieve partial or complete substitution of alkali ions into intercalation cathodes for alkali-ion batteries. In Na-ion cathodes, the partial substitution of Na for large, charge dense pillar ions, such as Ca<sup>2+</sup>, could help alleviate the detrimental structural transitions that these cathodes undergo during desodiation. Typically, ion-exchange is achieved by heating the cathode powder in the presence of a substantial molar excess of alkali halide salt in solution. Here, we successfully demonstrate ion-exchange of Ca<sup>2+</sup> for Na<sup>+</sup> in Na<sub>0.67</sub>Mn<sub>0.72</sub>Mg<sub>0.28</sub>O<sub>2</sub> by simple mechanical mixing of powders with the proper molar amount of CaI<sub>2</sub> under ambient conditions. The reaction proceeds in the solid-state at room temperature via the formation of crystalline hydrates of CaI<sub>2</sub> which form spontaneously with moisture in the air. Ca<sup>2+</sup> is uniformly incorporated into the layered cathode up to a limit of about 0.1 Ca (i.e. Na<sub>0.47</sub>Ca<sub>0.1</sub>Mn<sub>0.72</sub>Mg<sub>0.28</sub>O<sub>2</sub>). These findings point to the intriguing possibility of achieving facile room temperature, solid-state ion-exchange in other alkali-ion systems.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"434 ","pages":"Article 117085"},"PeriodicalIF":3.3,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145623404","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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